Biocidal agents



3,190,797 BIOCIDAL AGENTS Jakob Bindler, Riehen, near Basel, Ernst Model, Basel,

and Robert Zinkernagel, Riehen, near Basel, Switzer- 3,190,797 nted June 22, 1965 generally, also contain potassium salts of anion active wetting and cleaning agentswhich are soluble in oil, as well as for the production of so-called sprays. In addition, it can be mixed with pape r treatment liguids or land, assignors to Geigy Chemical Corporation, Ardsley, 5 printing thickeners of starch or cellulds'e ii'e'iivatives, or -a a orporation of Delaware it can be used for impregnating wood. Also an efiective N i f j 1960 49,818 protection against attacld b'yifiifigi"is bbtained with the sub- Clalms Prlonty, PP ;3 g7 1959 stance used according to the invention in polyvinyl chlosclainzs (Cl 167433) ride preparations, for example in sheets as well as lac- 10 quers and pai pis which are produced from a casein base This invention concerns biocidal agents, their use for or contain c'asein All these compositions characterised the protection of organic material from attack by fungi and by a content of fungicidal active substance of the general from damage by roll as well as, as industrial product, the formula given above are regarded as coming within the organic material protected by these agents from attack by scope of the process according to the invention. fungi and rot. Compared with the low halogenated 2,3-dihydrobenz- It has been found that 4,5,6,7-tetrach1oro-2,3-dihydrooxazole-Z-ones, the active substance used according to benzoxazole-Z-one of the formula the present invention has the advantage of being more active against fungi; however, it has a relatively good ac- 01 tion against bacteria also.

The fungicidal active substance is generally brought onto the organic material to be protected either by mix- O=0 ing, spraying or by impregnating with organic aqueous or aqueous/alkaline solutions of the active substance 4 O or with washing, cleaning or rinsing liquors containing 1 the active substance dissolved or dispersed therein. In g the 3 ggiitf iiaiiifiiiigfiol'1E2 .3asziati arrasaz teria rom attac by ungi an amage y r0 n e following, this property will be referred to a; iungicigfi gigg tignwgzi i 51:0?:g'etimrgagglsgegffgbgletltlfe astll 222g? gfi gg g g f 2:5: gi z l gg fig if gg a z i material can be still further increased by an after-treatalso include a fungistatic action ment with agents giving oif heavy metal. Copper salts, Also the tautomeric form namely, 4,5,6,7-tetrachloroexample can b used as Such agents Cellulose z hydroxybenzoxazole Suchas is formed by the replace terlal such as textiles, cellulose, wood and paper etc. are ment of hydrogen a the ring nitrogen atom to the the principal organic materials to be protected; refcarbonyl-oxygen atom, as well as the salts of this tau- P l bfien E l above P g use m Punt tomeric form, in particular the alkali metal salts or allsxo 2 5;gi gggg%%%fififfifigg g gffi where 3225: 223 salts are consldered as embraced by t e not otherwise expressly stated, parts are given as parts The 2 ,3-dihydrobenzoxazole-Z-one chlorine-substituted 40 g gg gz g g gz gfg g zis fi i 32: zgig g 1n the rmg whlch is used according to the invention is P P P y obtained, for example from 4,5,6,7-tetrachloro-2-aminoas that of grammes to cubic cemlmetres' phenol on reaction with phosgene. Example If desired the chlorine atoms can be introduced into 20 arts of 4,5,6,7-tetrachloro-2,3-dihydrobenzoxazolethe 23'dlhydrobenzoxazole'z'orie compound only after- Z-One and 10 parts of 30% caustic soda lye are dissolved wards, for example, unto 2,3-d1hydrobenzoxazole-Z-ones in 400 parts y volume of ethylene glycol monomethyl fi g i free 1 g gf s fg gi ether and this stock solution is diluted with water to y to enzoxazo use accqr mg 0 e mv n ion produce a treatment liquor which contains 0.5 g. of active 1s a colourless to weakly yellowish coloured substance Substance er litre which is only slightly soluble The alkali Calico is treated for 30 minutes at 40 in this liquor metal for examp lithium spdlum and Poms (liquor ratio 1:10), squeezed out until the increase in slum salts, also the magnesium or calclum salts, as well Wei ht is 72% and then dried cold The material so as the ammonium Salts of Strong inorganic or orgamc mtrea ied is rotected a ainst mildew s ots and rot as the trogen bases are much more easily soluble. Because of fonowin E p these solubility properties and because of their relatively Agildew s 0 test Circu1m attems of fabric of 9 good stability to alkalies, the chlorinated 2,3-dihydrobenzcm diameter i laced in etri (fishes on an a at oxazole'z'one used according to the invention Cain be trient medium and inoculat d with a suspensioi of a incorporated into textile treatment liquors in particular mixture of Spores of Penicillium expansum stachybohys in-to papilla-r31 active Washmg liquor-S Whlch can conatra and Aspergillus niger, which contains 40,000 germs tam, 1n addition to the usual synthetic wash-active subp ccm. The closed petri dishes are left for 10 y at stances and/or soaps, also the usual fillers such as sodium and then the number of fun i colonifis is counted carbonate, sodium silicates and alkali monoand poly- R t 1 Cr U1 i f fabric f phosphates as well as the other ingredients generally used cm g g g g 5 3 dishsesoon an gg in washing agents. It can be mixed direct wit such washing and cleansing agents and also with soap, and i f g zi gg g g z fssg x g gi fs gf g washing liquors are obtained w1th cleans1ng agents so P i co tgins'about 700 000 s r c It s 16 ft composed 3% protec mat/filed ig g z 5: 13:31 f0: 10 days at 28 the d evelop inent of the germs from attac -un i-an amage ere y. e su c1en solubility of tile active substances in organic solvents such is intemlllted l an Y S1ut10n, Pleces as are used in so-called dry cleaning, enables them to be 0f mammal an? rinsed and f Th6 mateflal 1S 6 used in dry cleaning agents consisting of aliphatic or tested in the spot tester according to R. Burgess (Microaromatic, possibly chlorinated, hydrocarbons and which, organismus and Textiles: The Journal of Applied Bac- 3 teriology 17, 241 (1954)), to see if the strength of the material has been reduced.

In the rotting test, the value given is the average of 10 tests. The strength is given in percent of the original strength of the material. The following results were obtained Content Mildew spot test, number of Rotting of treat; fungi colonies test; Substance merit strength,

liquor, percent g./litre Pen. exp. Stach. a. Asp. n.

According to example 0. 5 0 0 0 93 Blank test 0 w w m 0 What we claim is:

1. The method of protecting an organic substrata against fungi and bacteria which comprises applying thereto a composition of matter consisting essentially of 4,5,6,7- tetrachloro-2,3-dihydrobenzoxazole-2-one in solution in an organic aqueous carrier.

2. The method of protecting an organic substrata against fungi and bacteria which comprises applying thereto a composition of matter consisting essentially of 4,5,6,7-tetrachloro-2,3-dihydrobenzoxazole-Z-one in solution in an aqueous medium.

3. A cellulose material having an adherent coating consisting essentially of 4,5,6,7-tetrachloro-2,3-dihydro benzoxaole-Z-one, whereby the said material is protected against fungi and bacteria.

References Cited by the Examiner UNITED STATES PATENTS 2,041,513 5/36 Raeck 260307.3 2,583,425 1/52 Hawley 167--30 2,922,794 1/ 60 Model et al. 167-33 2,999,047 9/61 Model et a1. 16733 JULIAN S, LEVITT, Primary Examiner.

20 WILLIAM B. KNIGHT, MORRIS O, WOLK, IRVING MARCUS, Examiners. 

2. THE METHOD OF PROTECTING AN ORGANIC SUBSTRATA AGAINST FUNGI AND BACTERIA WHICH COMPRISES APPLYING THERETO A COMPOSITION OF MATTER CONSISTING ESSENTIALLY OF 4,5,6,7-TETRACHLORO-2,3-DIHYDROBENZOXAZOLE-2-ONE IN SOLUTION IN AN AQUEOUS MEDIUM. 